Feb 10, 2006

Energetics from slow infrared multiphoton dissociation of biomolecules

The Journal of Physical Chemistry. a
Rebecca A JockuschEvan R Williams


Photodissociation kinetics of the protonated pentapeptide leucine enkephalin measured using a cw CO(2) laser and a Fourier-transform mass spectrometer are reported. A short induction period, corresponding to the time required to raise the internal energy of the ion population to a (dissociating) steady state, is observed. After this induction period, the dissociation data are accurately fit by first-order kinetics. A plot of the log of the unimolecular dissociation rate constant, k(uni), as a function of the log of laser power is linear at low laser powers (<9 W, k(uni) <0.05 s(-1)), but tapers off at high laser power (9-33 W, k(uni) = 0.05-7 s(-1)). The entire measured dissociation curve can be accurately fit by an exponential function plus a constant. The experiment is simulated using a master equation formalism. In the model, the laser radiation is described as an energetically flat-topped distribution which is spatially uniform. This description is consistent with experimental results which indicate that ion motion within the cell averages out spatial inhomogeneities in the laser light. The model has several adjustable parameters. The effect of varying these parameters on the calculated kinetics and power dependence curves ...Continue Reading

Mentioned in this Paper

Dissociative Disorder
Enkephalin, Leucine

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